Electrode-electrolyte components, electrochemical cells, electrochemical accumulators and their uses

Abstract

The present technology relates to the modification of the surface of an electrode to include a thin layer, e.g., 10 microns or less, of an inorganic compound (such as a ceramic) in a solid polymer, where the inorganic compound is present in the thin layer at a concentration between about 40% and about 90% by weight. Electrodes including the modified membrane, components including the electrode and a solid electrolyte, and electrochemical cells and accumulators including the same are also described. The present application relates to lithium electrodes having at least one modified surface, processes for their manufacture, and electrochemical cells including them.

Description

[Technical Field]

[0001] Related applications This application claims priority under applicable law to Canadian Patent Application No. 3,072,784, filed on 14 February 2020, the contents of which are incorporated herein by reference in their entirety for all purposes.

[0002] Technical field This application relates to lithium electrodes having at least one modified surface, a process for manufacturing them, and an electrochemical cell containing them. [Background technology]

[0003] Technical background The liquid electrolyte used in lithium-ion batteries is flammable and slowly decomposes, forming a passivation layer on the surface of the lithium membrane or at the interface with the solid electrolyte ("solid electrolyte interface" or "solid electrolyte interface phase" SEI), irreversibly consuming lithium and reducing the battery's Coulombic efficiency. Furthermore, the lithium anode undergoes significant morphological changes during battery cycling, forming lithium dendrites. These typically migrate through the electrolyte, potentially leading to short circuits. Safety concerns and the demand for higher energy density have fueled research into the development of all-solid-state lithium secondary batteries, both of which are more stable with respect to lithium metal and reduce lithium dendrite growth. However, loss of reactivity and poor contact between solid interfaces remain problems in these all-solid-state batteries.

[0004] A simpler and more industrially available method for protecting lithium surfaces is to coat them with a polymer or polymer / lithium salt mixture by using spraying, dipping, centrifugation, or the so-called doctor blade method (N. Delaporte et al., Front. Mater., 2019, 6, 267). The selected polymer must be stable against lithium and ionic conductors at low temperatures. In a sense, the polymer layer deposited on the lithium surface remains rubbery at room temperature and maintains low glass transition (T) to preserve lithium conductivity similar to that of a liquid electrolyte. g It should be comparable to solid polymer electrolytes (SPEs) commonly reported in the literature, possessing the following properties. To accommodate the deformation of lithium during cycling, and especially to avoid the formation of lithium dendrites, the polymer must have good flexibility and be characterized by a high Young's modulus.

[0005] A few examples of polymers used in this type of protective layer include polyacrylic acid (PAA) (N.-W.Li et al., Angew. Chem. Int. Ed., 2018, 57, 1505-1509), poly(vinylidene carbonate-co-acrylonitrile) (SMChoi et al., J. Power Sources, 2013, 244, 363-368), and poly(ethylene glycol) dimethacrylate (YMLee et al., J. Power Sources, 2003, 119-121, 964-972), PEDOT-co-PEG copolymer (G. Ma et al., J. Mater. Chem. A, 2014, 2, 19355-19359 and ISKang et al., J. Electrochem. Soc., 2014, 161(1), A53-A57), polymer obtained from direct polymerization of acetylene on lithium (DGBelov et al., Synth. Met., 2006, 156, 745-751), in situ-polymerized ethyl α-cyanoacrylate (Z. Hu et al., Chem. Mater., 2017, 29, 4682-4689), and polymer formed from copolymer Kynar® 2801 and curable monomer 1,6-hexanediol diacrylate (N.-S. Choi et al., Solid State One example is Ion., 2004, 172, 19-24). The latter group also investigated the incorporation of ion acceptors into polymer mixtures (N.-S. Choi et al., Electrochem. Commun., 2004, 6, 1238-1242).

[0006] Several studies have been conducted on incorporating solid fillers, typically ceramics, into polymers for lithium surface modification. For example, by mixing inorganic fillers (e.g., Al2O3, TiO2, BaTiO3) with polymers, hybrid organic-inorganic composite electrolytes have been obtained.

[0007] A mixture of newly synthesized spherical Cu3N particles with a diameter of less than 100 nm and styrene-butadiene rubber (SBR) copolymer was applied to a lithium surface using a doctor blade (Y. Liu et al., Adv. Mater., 2017, 29, 1605531). Upon contact with lithium, Cu3N is converted to highly lithium-conductive Li3N. Li4Ti5O 12 By assembling a Li(LTO / Li) cell with a liquid electrolyte and using lithium protected by a mixture of Cu3N and SBR, better electrochemical performance was obtained.

[0008] To improve the lifespan of lithium-oxygen batteries, a 20 μm protective layer consisting of Al2O3 particles (average diameter 1.7 μm) deposited on the lithium surface and polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) has been proposed (DJ Lee et al., Electrochem.Commun., 2014, 40, 45-48). This protective layer and liquid electrolyte were used in a Co3O4-Super P / Li battery. The effects of similarly modified lithium have also been investigated by Gao and his collaborators (HK Jing et al., J.Mater.Chem.A, 2015, 3, 12213-12219), but the focus has been on improving lithium-sulfur batteries. In this example, 100 nm Al2O3 spheres were used as a binder with PVDF, and the mixture prepared in DMF solvent was spin-coated onto lithium foil. The battery was then assembled using a liquid electrolyte.

[0009] To limit the growth of lithium, a 25-μm porous layer (particle size of about 10 nm) of polyimide containing Al2O3 as a filler has also been proposed (see Z. Peng et al., J. Mater. Chem. A, 2016, 4, 2427-2432). This method involves forming a film called a "skin layer" by contacting lithium with additives (such as fluoroethylene carbonate (FEC), vinylene carbonate (VC) or hexamethylene diisocyanate (HDI), etc.) present in the liquid electrolyte. Tests were carried out on a Cu / LiFePO4 electrochemical cell containing this liquid electrolyte to demonstrate the usefulness of the polyimide / Al2O3 layer in suppressing dendrite formation and electrolyte decomposition. The protective layers described in the previous three paragraphs are porous and are suitable for use with a liquid electrolyte that can penetrate them. Therefore, this type of layer must be able to contact the surface of the electrode (or its protective layer) closely and is not suitable for use with a solid electrolyte that must conduct ions from the electrolyte to the electrode active material.

Prior Art Documents

Non-Patent Documents

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Summary of the Invention

Means for Solving the Problems

[0011] Summary According to a first aspect, the present technology relates to an electrode including a metal film modified by a thin layer, - the metal film includes lithium or an alloy containing lithium, and the metal film includes a first and a second surface; and - The thin layer comprises an inorganic compound in a solvated polymer (e.g., a solid polymer and / or a crosslinked polymer), the thin layer is placed on a first surface of a metal film, and has an average thickness of about 10 μm or less (or between about 0.5 μm and about 10 μm, or between about 1 μm and about 10 μm, or between about 2 μm and about 8 μm, or between about 2 μm and about 7 μm, or between 2 μm and about 5 μm), and the inorganic compound is present in the thin layer at a concentration between about 40% by weight and about 90% by weight.

[0012] In one embodiment, the metal film comprises lithium containing impurities in amounts less than 1000 ppm (or less than 0.1 wt%). In another embodiment, the metal film comprises an alloy of lithium with an element selected from alkali metals other than lithium (such as Na, K, Rb, and Cs), alkaline earth metals (such as Mg, Ca, Sr, and Ba), rare earth metals (such as Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), zirconium, copper, silver, bismuth, cobalt, manganese, zinc, aluminum, silicon, tin, antimony, cadmium, mercury, lead, molybdenum, iron, boron, indium, thallium, nickel, and germanium (e.g., Zr, Cu, Ag, Bi, Co, Zn, Al, Si, Sn, Sb, Cd, Hg, Pb, Mn, B, In, Tl, Ni, or Ge). For example, the alloy contains at least 75% by weight of lithium, or between 85% and 99.9% by weight of lithium.

[0013] According to another embodiment, the metal film further comprises a passivation layer on a first surface, the first surface being in contact with a thin layer, for example, the passivation layer comprising a compound selected from silanes, phosphonates, borates, or inorganic compounds (such as LiF, Li3N, Li3P, LiNO3, Li3PO4).

[0014] In another embodiment, the first surface of the metal film is modified beforehand by stamping.

[0015] In one embodiment, the inorganic compound is in the form of particles (e.g., spherical, rod-shaped, needle-shaped, etc.). In another embodiment, the average particle size is less than 1 μm, less than 500 nm, or less than 300 nm, or less than 200 nm, or between 1 nm and 500 nm, or between 10 nm and 500 nm, or between 50 nm and 500 nm, or between 100 nm and 500 nm, or between 1 nm and 300 nm, or between 10 nm and 300 nm, or between 50 nm and 300 nm, or between 100 nm and 300 nm, or between 1 nm and 200 nm, or further between 50 nm and 200 nm, or between 100 nm and 200 nm, or between 1 nm and 100 nm, or further between 25 nm and 100 nm, or between 50 nm and 100 nm.

[0016] According to one embodiment, the inorganic compound includes ceramics. According to another embodiment, the inorganic compound is Al2O3, Mg2B2O5, Na2O·2B2O3, xMgO·yB2O3·zH2O, TiO2, ZrO2, ZnO, Ti2O3, SiO2, Cr2O3, CeO2, B2O3, B2O, SrBi4Ti4O 15 LLTO, LLZO, LAGP, LATP, Fe2O3, BaTiO3, γ-LiAlO2, molecular sieves and zeolites (e.g., aluminosilicate, mesoporous silica), sulfide ceramics (Li7P3S 11 The materials selected are glass ceramics (such as LIPON), other ceramics, and combinations thereof.

[0017] In yet another embodiment, the inorganic compound particles further include organic groups covalently grafted onto their surface, for example, the groups being selected from crosslinkable groups (such as organic groups including acrylate functional groups, methacrylate functional groups, vinyl functional groups, glycidyl functional groups, mercapto functional groups, etc.), aryl groups, alkylene oxide groups or poly(alkylene oxide) groups, and other organic groups.

[0018] In one embodiment, the particles of the inorganic compound have a small specific surface area (for example, 80 m²). 2 Less than / g, or 40m 2 The inorganic compound has a specific surface area (less than / g), and preferably, the inorganic compound is present in the thin layer at a concentration between about 65% and about 90% by weight, or between about 70% and about 85% by weight. Alternatively, the particles of the inorganic compound have a large specific surface area (e.g., 80m²). 2 / g and above, or 120m 2 The inorganic compound has a concentration of (and more than) / g, and preferably, is present in the thin layer at a concentration between about 40% and about 65% by weight, or between about 45% and about 55% by weight.

[0019] According to another embodiment, the solvated polymer is selected from linear or branched polyether polymers (e.g., PEO, PPO, or EO / PO copolymers), poly(dimethylsiloxane), poly(alkylene carbonate), poly(alkylene sulfone), poly(alkylene sulfamide), polyurethane, poly(vinyl alcohol), polyacrylonitrile, poly(methyl methacrylate), and their copolymers, and optionally includes crosslinking units derived from crosslinkable functional groups (such as acrylate functional groups, methacrylate functional groups, vinyl functional groups, glycidyl functional groups, mercapto functional groups, etc.).

[0020] In another embodiment, the thin layer may be, for example, lithium hexafluorophosphate (LiPF6), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 2-trifluoromethyl-4,5-dicyanoimidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium tetrafluoroborate (LiBF4), lithium bis(oxalato)borate (LiBOB), lithium nitrate (LiNO3), lithium chloride (Li The present invention further includes lithium salts selected from LiCl), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (LiClO4), lithium hexafluoroarsenate (LiAsF6), lithium trifluoromethanesulfonate (LiSO3CF3) (LiTf), lithium fluoroalkyl phosphate Li[PF3(CF2CF3)3] (LiFAP), lithium tetrakis(trifluoroacetoxy)borate Li[B(OCOCF3)4] (LiTFAB), lithium bis(1,2-benzenediolato(2-)-O,O')borate Li[B(C6O2)2] (LBBB), and combinations thereof.

[0021] According to another embodiment, the electrode further includes a current collector that contacts a second surface of the metal film.

[0022] Another embodiment relates to an electrode including an electrode material film modified by a thin layer, - The electrode material film comprises an electrochemical active material, a binder if necessary, and an electronically conductive material if necessary, and the electrode material film comprises a first and a second surface, and - The thin layer contains an inorganic compound in a solvated polymer (e.g., a solid polymer and / or a cross-linked polymer), the thin layer is disposed on the first surface of the metal film, has an average thickness of about 10 μm (or between about 0.5 μm and about 10 μm, or between about 1 μm and about 10 μm, or between about 2 μm and about 8 μm, or between about 2 μm and about 7 μm, or between 2 μm and about 5 μm) or less, and the inorganic compound is present in the thin layer at a concentration between about 40 wt% and about 90 wt%.

[0023] According to one embodiment, elements of the thin layer (inorganic compound, polymer, and optionally salt) defined in the embodiments of the above-described aspect are also contemplated.

[0024] In another embodiment, the electrode further includes a current collector in contact with the second surface of the electrode material film.

[0025] According to another embodiment, the electrochemically active material is selected from metal phosphates, lithiated metal phosphates, metal oxides, and lithiated metal oxides. In another embodiment, the electrochemically active material is LiM’PO4 (where M’ is Fe, Ni, Mn, Co, or a combination thereof), LiV3O8, V2O5F, LiV2O5, LiMn2O4, LiM’’O2 (where M’’ is Mn, Co, Ni, or a combination thereof (NMC, LiMn x Co y Ni zCarbon-based active materials such as O2 (wherein x+y+z=1), Li(NiM''')O2 (wherein M''' is Mn, Co, Al, Fe, Cr, Ti, Zr, or a combination thereof), sulfur, selenium, iodine, iron(III) fluoride, copper(II) fluoride, lithium iodide, graphite, organic cathode active materials such as polyimide, poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PTMA), tetra-lithium perylene-3,4,9,10-tetracarboxylate (PTCLi4), naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA), perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA), π-conjugated dicarboxylates, and anthraquinones, or any combination of two or more of these materials where compatible with each other.

[0026] In yet another embodiment, the electrochemical active material is in the form of particles that are optionally coated (for example, by polymers, ceramics, carbon, or a combination of two or more thereof).

[0027] In another embodiment, this specification describes electrode-electrolyte components including electrodes and solid electrolytes as defined herein. In one embodiment, the solid electrolyte comprises at least one solvated polymer and a lithium salt.

[0028] In one embodiment, the solvating polymer of the electrolyte is selected from linear or branched polyether polymers (e.g., PEO, PPO, or EO / PO copolymers) and optionally includes crosslinkable units, poly(dimethylsiloxane), poly(alkylene carbonate), poly(alkylene sulfone), poly(alkylene sulfamide), polyurethane, poly(vinyl alcohol), polyacrylonitrile, poly(methyl methacrylate), and copolymers thereof, and the solvating polymer is optionally crosslinked.

[0029] In another embodiment, the lithium salt of the electrolyte is lithium hexafluorophosphate (LiPF6), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 2-trifluoromethyl-4,5-dicyanoimidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium tetrafluoroborate (LiBF4), lithium bis(oxalato)borate (LiBOB), lithium nitrate (LiNO3), lithium The following are selected: chloride (LiCl), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (LiClO4), lithium hexafluoroarsenate (LiAsF6), lithium trifluoromethanesulfonate (LiSO3CF3) (LiTf), lithium fluoroalkyl phosphate Li[PF3(CF2CF3)3] (LiFAP), lithium tetrakis(trifluoroacetoxy)borate Li[B(OCOCF3)4] (LiTFAB), lithium bis(1,2-benzenediolato(2-)-O,O')borate Li[B(C6O2)2] (LBBB), and combinations thereof.

[0030] Further embodiments of this specification relate to an electrochemical cell comprising a negative electrode, a positive electrode, and a solid electrolyte, wherein at least one of the negative electrode and the positive electrode is as described herein. In one embodiment, the negative electrode is as described herein. In another embodiment, the positive electrode is as described herein. Alternatively, the negative electrode and the positive electrode are as described herein. In one embodiment, the electrolyte is as defined above.

[0031] Finally, the technology also includes electrochemical accumulators (e.g., lithium batteries or lithium-ion batteries) comprising at least one electrochemical cell as described herein, as well as their use in portable devices (such as mobile phones, cameras, tablets or laptops), electric or hybrid vehicles, or renewable energy storage. [Brief explanation of the drawing]

[0032] [Figure 1] Figure 1 shows a photograph of a cross-section of a lithium piece having a ceramic thin layer (85% spherical Al2O3).

[0033] [Figure 2] Figure 2 shows a scanning electron microscope (SEM) image of a thin layer containing 50% Mg2B2O5 on a LiAl alloy (a) and its corresponding chemical mapping: (b) magnesium, (c) boron, (d) oxygen, (e) sulfur, (f) fluorine, and (g) carbon.

[0034] [Figure 3] Figure 3 shows SEM images of thin layers containing ceramic (85% spherical Al2O3) on a LiMg alloy, showing a ceramic-rich layer and a polymer-rich layer.

[0035] [Figure 4] Figure 4 shows an SEM image (a) of a thin layer containing 50% needle-shaped Al2O3 on a LiAl alloy, along with its corresponding chemical mapping: (b) C, Al, O, S and electron distribution, (c) aluminum, (d) oxygen, and (e) carbon.

[0036] [Figure 5] Figure 5 shows SEM images (top image) of an SPE (approximately 15-20 μm) containing spherical Al2O3 ceramic (70 wt%) on a LiAl alloy, as well as the distribution of S, C, Al, O, and electrons (bottom image).

[0037] [Figure 6] Figure 6 shows SEM images (top image) and S, C, Al, O, and electron distribution (bottom image) of an SPE (approximately 10-15 μm) containing spherical Al2O3 ceramic (85 wt%) on a LiAl alloy.

[0038] [Figure 7] SEM images ((a) and (b)) of a symmetric Li / SPE / Li cell prepared with standard unmodified Li, along with its chemical mapping: (c) carbon, (d) oxygen, (e) fluorine, (f) lithium, (g) sulfur, and (h) aluminum (Al from the support behind the sample).

[0039] [Figure 8-1] (a) Spectral impedance measurements of four cells; (b) Cycle stability results at C / 4 rates (charge and discharge) for two cells (including two C / 24 formation cycles); and (c) Resistance results at different applied currents (C / 24 to 1C) for two independent cells. All cells are symmetrical and assembled with standard pure lithium. [Figure 8-2] Same as above.

[0040] [Figure 9-1] (a) Spectral impedance measurements of four cells; (b) Cycle stability results at C / 4 rates (charge and discharge) for two cells (including two C / 24 formation cycles); and (c) Resistance results at different applied currents (C / 24 to 1C) for two independent cells. All cells are symmetrical and assembled from LiAl lithium alloy. [Figure 9-2] Same as above.

[0041] [Figure 10-1] (a) Spectral impedance measurements of four cells; (b) Cycle stability results at C / 4 rates (charge and discharge) for two cells (including two C / 24 formation cycles); and (c) Resistance results at different applied currents (C / 24 to 1C) for two independent cells. All cells are symmetrical and assembled from LiMg lithium alloy. [Figure 10-2] Same as above.

[0042] [Figure 11] Figure 11 shows SEM images of a symmetric LiAl / SPE / LiAl cell assembled with standard Li modified with spherical Al2O3 (85 wt%) at various magnifications.

[0043] [Figure 12] Figure 12 shows an SEM image ((a)) of a symmetric LiAl / SPE / LiAl cell assembled with standard Li modified with spherical Al2O3 (85 wt%), and its chemical mapping: (b) oxygen, (c) aluminum, (d) carbon, (e) fluorine, (f) sulfur, and (g) lithium.

[0044] [Figure 13-1] Figure 13 shows (a) the resistance results for two LiAl batteries assembled at different applied currents (C / 24 to 1C); (b) and (c) the results of spectral impedance measurements performed at 50°C for the two batteries after assembly and after each cycling rate. All batteries are symmetrical and LiAl modified with spherical Al2O3 (85 wt%). [Figure 13-2] Same as above.

[0045] [Figure 14-1] Figure 14 shows (a) and (b) cycle stability studies at a 1C rate (charge and discharge), including a return to a C / 4 rate, over three cycles of two independent cells; and (c) and (d) results of spectral impedance measurements performed every three cycles at 50°C on the same cells. All batteries are symmetrical and made of LiAl modified with spherical Al2O3 (85 wt%). [Figure 14-2] Same as above.

[0046] [Figure 15]Figure 15 shows SEM images ((a)) and chemical mappings of symmetric LiAl / SPE / LiAl cells prepared with standard Li modified with spherical Al2O3 (85 wt%), as well as (b) oxygen, (c) carbon, (d) aluminum, (e) fluorine, (f) sulfur, and (g) lithium (symmetric cell with short circuit).

[0047] [Figure 16-1] Figure 16 shows (a) spectral impedance measurements of four cells; (b) cycle stability results at C / 4 rates (charge and discharge) for two cells (including two C / 24 formation cycles); and (c) resistance results at different applied currents (C / 24 to 1C) for two independent cells. All cells are symmetrical and assembled with spherical Al2O3-reformed lithium (85 wt%). [Figure 16-2] Same as above.

[0048] [Figure 17-1] Figure 17 shows (a) spectral impedance measurements of three cells; (b) cycle stability results at C / 4 rates (charge and discharge) for one cell (including two C / 24 formation cycles); and (c) resistance results at different applied currents (C / 24 to 1C) for two independent cells. All cells are symmetrical and assembled with needle-shaped Al2O3-modified lithium (50 wt%). [Figure 17-2] Same as above.

[0049] [Figure 18-1] Figure 18 shows a scheme illustrating a configuration assembled with (a) needle-shaped Al2O3-modified LiAl (50 wt%) on one side and unmodified LiAl on the other, as well as results obtained with these cells, including (b) spectral impedance measurements of four cells; (c) cycle stability results in the C / 4 regime (charge and discharge) of two cells (including two C / 24 formation cycles); and (d) resistance results at different applied currents (C / 24 to 1C) of two independent cells. [Figure 18-2] Same as above.

[0050] [Figure 19] Figure 19 shows SEM images ((a) and (b)) of a battery (without short circuits) assembled with LiAl modified on one side with needle-shaped Al2O3 (50 wt%) and the other side with unmodified LiAl, as well as its chemical mapping: (c) carbon, (d) oxygen, (e) aluminum, (f) fluorine, (g) sulfur, and (h) lithium.

[0051] [Figure 20] Figure 20 shows SEM images ((a), (b), and (c)) of a battery (with a short circuit) assembled with LiAl modified on one side with needle-shaped Al2O3 (50 wt%) and the other side with unmodified LiAl, as well as its chemical mapping: (d) carbon, (e) oxygen, (f) fluorine, (g) aluminum, (h) sulfur, and (i) lithium.

[0052] [Figure 21] Figure 21 shows (a) a schematic diagram of a stack assembly having a layer of approximately 25 μm thickness on which a LiAl film is directly deposited on its surface containing 85% spherical Al2O3; (b) spectral impedance measurements performed at 50°C on two independent stacks; and (c) the first two C / 24 formation cycles of two cells assembled according to the schematic diagram in (a).

[0053] [Figure 22-1] (a) The first two charge / discharge curves obtained at 80°C and C / 24 for an LFP / SPE / LiAl battery assembled using an unmodified LiAl anode; (b) a LiAl anode with a layer containing 50% needle-shaped Al2O3; and (c) a LiAl anode with a layer containing 85% spherical Al2O3. [Figure 22-2] Same as above.

[0054] [Figure 23-1]Figure 23 shows the constant current cycling results obtained at 50°C and C / 6 (every 20 cycles at C / 6 and every 2 cycles at C / 12) for LFP / SPE / LiAl batteries assembled using (a) an unmodified LiAl anode; (b) a LiAl anode with 50% needle-shaped Al2O3; and (c) a LiAl anode with a layer containing 85% spherical Al2O3. [Figure 23-2] Same as above.

[0055] [Figure 24] Figure 24 shows the constant current cycling results obtained at 50°C and C / 6 (every 20 cycles at C / 6 and every 2 cycles at C / 12) for LFP / SPE / LiMg batteries assembled using (a) an unmodified LiMg anode and (b) a LiMg anode having a layer containing 85% spherical Al2O3.

[0056] [Figure 25] Figure 25 shows the constant current cycling results obtained at 50°C and C / 6 (every 20 cycles at C / 6 and every 2 cycles at C / 12) for LFP / SPE / Li batteries assembled using (a) an unmodified Li anode and (b) a Li anode having a layer containing 85% spherical Al2O3.

[0057] [Figure 26] Figure 26 shows SEM images (500x on the left, 5000x on the right) of thin layers of polymer and salt (without ceramic) on a composite material containing LiFePO4.

[0058] [Figure 27] Figure 27 shows SEM images (a) of thin layers of polymer and salt (without ceramic) on a composite material containing LiFePO4, along with their corresponding chemical mappings: (b) iron, (c) phosphorus, (d) oxygen, (e) carbon, and (f) sulfur.

[0059] [Figure 28]Figure 28 shows an SEM image of the edge of an LFP cathode having a polymer + salt (20:1 O:Li) thin layer containing 50 wt% spherical Al2O3.

[0060] [Figure 29] Figure 29 shows SEM images of the edges of an LFP cathode having a polymer + salt (20:1 O:Li) thin layer containing 50 wt% spherical Al2O3 (a), as well as its corresponding chemical mappings for (b) phosphorus, (c) iron, (d) oxygen, (e) carbon, and (f) aluminum.

[0061] [Figure 30] Figure 30 shows the results of (a) long-term cycling (charge: C / 6, discharge: C / 3) and (b) cycling at different C rates at 80°C for LFP / SPE / Li batteries assembled using standard (unmodified) LiAl, standard SPE (polymer + LiTFSI with an O:Li ratio of 30:1 and a thickness of 20 μm), and LFP cathodes with and without a ceramic thin layer (50% Al2O3) (overcoat LFP). [Modes for carrying out the invention]

[0062] Detailed explanation All technical and scientific terms and expressions used herein have the same meaning as those generally understood by those skilled in the art. Nevertheless, some definitions of the terms and expressions used are given below.

[0063] When the term "approximately" is used here, it means roughly within and around a given area. When the term "approximately" is used in relation to a number, it means that it can be changed up or down by, for example, 10% of its nominal value. This term may also take into account, for example, experimental errors or rounding of values ​​inherent in the measuring instrument.

[0064] Where a range of values ​​is referred to in this application, the lower and upper limits of the range are always included in the definition unless otherwise specified. For example, "between x and y" or "of x to y" means a range that includes the limits of x and y unless otherwise specified. For example, the range "between 1 and 50" includes the values ​​1 and 50.

[0065] The chemical structures described herein are drawn in accordance with the conventions of the art. Furthermore, where atoms such as carbon atoms appear to have incomplete valencies, those valencies are considered to be filled by one or more hydrogen atoms, even if they are not explicitly depicted.

[0066] As used herein, the term “alkyl” refers to a saturated hydrocarbon group having 1 to 20 carbon atoms, including linear or branched alkyl groups. Non-limiting examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, tert-butyl, sec-butyl, and isobutyl. Similarly, an “alkylene” group refers to an alkyl group located between two other groups. Examples of alkylene groups include methylene, ethylene, and propylene. n "Alkyl" and "C1-C n The term "alkylene" refers to an alkyl group or alkylene group having 1 to n carbon atoms.

[0067] Accordingly, this specification describes a process for surface modification of electrode films. In one example, the electrode film includes a metal film containing, for example, lithium or a lithium-based alloy. In another example, the electrode film includes an electrochemical active material, a binder if necessary, and an electronically conductive material if necessary. Surface modification means the application of an ion-conducting thin layer that acts as a barrier against dendrite formation but substantially does not react with the surface of the electrode film because the elements of the thin layer are mainly non-reactive.

[0068] The surface of the electrode film is modified by applying a thin layer containing an inorganic compound in a solvating polymer, preferably a solid, and optionally a crosslinked polymer, to one of its surfaces. The thin layer is placed on the first surface of the metal film and has an average thickness of about 10 μm or less. The inorganic compound is present in the thin layer at a concentration ranging from about 40% to about 90% by weight.

[0069] The inorganic compound is preferably in the form of particles (e.g., spherical, rod-shaped, needle-shaped, etc.). The average particle size is preferably nanometers, for example, less than 1 μm, less than 500 nm, or less than 300 nm, or less than 200 nm, or between 1 nm and 500 nm, or between 10 nm and 500 nm, or further between 50 nm and 500 nm, or between 100 nm and 500 nm, or between 1 nm and 300 nm, or further between 50 nm and 300 nm, or between 100 nm and 300 nm, or between 1 nm and 200 nm, or between 10 nm and 200 nm, or between 50 nm and 200 nm, or between 100 nm and 200 nm, or between 1 nm and 100 nm, or further between 25 nm and 100 nm, or between 50 nm and 100 nm.

[0070] Non-limiting examples of inorganic compounds include compounds or ceramics, such as Al2O3, Mg2B2O5, Na2O·2B2O3, xMgO·yB2O3·zH2O, TiO2, ZrO2, ZnO, Ti2O3, SiO2, Cr2O3, CeO2, B2O3, B2O, SrBi4Ti4O 15 LLTO, LLZO, LAGP, LATP, Fe2O3, BaTiO3, γ-LiAlO2, molecular sieves and zeolites (e.g., aluminosilicate, mesoporous silica, etc.), sulfide ceramics (Li7P3S 11 Examples include glass ceramics (such as LIPON), other ceramics, and combinations thereof.

[0071] The surface of inorganic compound particles can also be modified by organic groups covalently grafted onto their surface. For example, the groups can be selected from crosslinking groups, aryl groups, alkylene oxide or poly(alkylene oxide) groups, and other organic groups, which are grafted onto the surface directly or via linking groups.

[0072] For example, the crosslinkable group may include glycidyl, mercapto, vinyl, acrylate, or methacrylate functional groups. An example of a method for grafting a silane containing a propyl methacrylate moiety is shown in Scheme 1. [ka]

[0073] In some cases, inorganic compound particles have a small specific surface area (for example, 80 m²). 2 Less than / g, or 40m 2 It has less than / g. The concentration of the inorganic compound in the thin layer may be relatively high, for example, between about 65% and about 90% by weight, or between about 70% and about 85% by weight.

[0074] In other cases, inorganic compound particles have a large specific surface area (for example, 80 m²). 2 / g and above, or 120m 2 The porosity of the inorganic compound is higher, which may require a larger amount of polymer, and the concentration of the inorganic compound in the thin layer may be in the range of 40% to about 65% by weight, or between about 45% and about 55% by weight.

[0075] As described above, the average thickness of the thin layer is considered to be due to the modification of the electrode surface, rather than the electrolyte layer. As mentioned above, the average thickness of the thin layer is less than 10 μm. For example, the average thickness is between approximately 0.5 μm and approximately 10 μm, or between approximately 1 μm and approximately 10 μm, or between approximately 2 μm and approximately 8 μm, or between approximately 2 μm and approximately 7 μm, or further between 2 μm and approximately 5 μm.

[0076] The polymers present in the layer are crosslinked polymers, particularly those containing ionic solvation units of lithium ions. Examples of solvation polymers include linear or branched polyether polymers (e.g., PEO, PPO, or EO / PO copolymers), poly(dimethylsiloxane), poly(alkylene carbonate), poly(alkylene sulfone), poly(alkylene sulfamide), polyurethane, poly(vinyl alcohol), polyacrylonitrile, poly(methyl methacrylate), and their copolymers, which may optionally contain crosslinking units derived from crosslinkable functional groups (e.g., acrylate functional groups, methacrylate functional groups, vinyl functional groups, glycidyl functional groups, mercapto functional groups, etc.).

[0077] In a preferred example, the thin layer further contains lithium salts. Non-limiting examples of lithium salts include lithium hexafluorophosphate (LiPF6), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 2-trifluoromethyl-4,5-dicyanoimidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium tetrafluoroborate (LiBF4), lithium bis(oxalato)borate (LiBOB), lithium nitrate (LiNO3), and lithium Examples include lithium chloride (LiCl), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (LiClO4), lithium hexafluoroarsenate (LiAsF6), lithium trifluoromethanesulfonate (LiSO3CF3) (LiTf), lithium fluoroalkyl phosphate Li[PF3(CF2CF3)3] (LiFAP), lithium tetrakis(trifluoroacetoxy)borate Li[B(OCOCF3)4] (LiTFAB), and / or lithium bis(1,2-benzenediolato(2-)-O,O')borate Li[B(C6O2)2] (LBBB).

[0078] As described above, the electrodes may include a metallic lithium film or a lithium-containing alloy on the current collector as needed. If the metallic film is a lithium film, the lithium film consists of lithium with less than 1000 ppm (or less than 0.1 wt%) of impurities. Alternatively, the lithium alloy may contain at least 75 wt% lithium, or between 85 wt% and 99.9 wt% lithium. The alloy may then contain elements selected from alkali metals other than lithium (such as Na, K, Rb, and Cs), alkaline earth metals (such as Mg, Ca, Sr, and Ba), rare earth metals (such as Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), zirconium, copper, silver, bismuth, cobalt, manganese, zinc, aluminum, silicon, tin, antimony, cadmium, mercury, lead, molybdenum, iron, boron, indium, thallium, nickel, and germanium (e.g., Zr, Cu, Ag, Bi, Co, Zn, Al, Si, Sn, Sb, Cd, Hg, Pb, Mn, B, In, Tl, Ni, or Ge).

[0079] The metal film may also include a passivation layer on the first surface in contact with the thin layer. For example, the passivation layer may contain a compound selected from silanes, phosphonates, borates, or inorganic compounds (such as LiF, Li3N, Li3P, LiNO3, Li3PO4, etc.). For example, the passivation layer may be formed on the metal film before the thin layer is added.

[0080] The surface of the metal film can also be treated before the application of the thin layer, for example, by stamping.

[0081] As described above, when the electrode is not a metal film, the electrode includes an electrochemical active material (e.g., the positive electrode), a binder if necessary, and an electronically conductive material if necessary, on the current collector if necessary. For example, the electrochemical active material may be selected from metal phosphates, lithified metal phosphates, metal oxides, and lithified metal oxides, but other materials may also be selected, such as elemental sulfur, selenium or iodine, iron(III) fluoride, copper(II) fluoride, lithium iodide, and carbon-based active materials such as graphite. Examples of electrochemical active materials include LiM'PO4 (wherein M' is Fe, Ni, Mn, Co, or a combination thereof), LiV3O8, V2O5F, LiV2O5, LiMn2O4, LiM''O2 (wherein M'' is Mn, Co, Ni, or a combination thereof (NMC, LiMn x Co y Ni z O2 (where x+y+z=1 in the equation, etc.) Carbon-based active materials such as ), Li(NiM''')O2 (wherein M''' is Mn, Co, Al, Fe, Cr, Ti, Zr, or a combination thereof), sulfur, selenium, iodine, iron(III) fluoride, copper(II) fluoride, lithium iodide, graphite, organic cathode active materials such as polyimide, poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PTMA), tetra-lithium perylene-3,4,9,10-tetracarboxylate (PTCLi4), naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA), perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA), π-conjugated dicarboxylates, and anthraquinones, or combinations of two or more of these materials when compatible with each other and a counter electrode, such as a lithium electrode. The electrochemical active material is preferably in the form of particles that can be coated as needed with, for example, polymers, ceramics, carbon, or a combination of two or more thereof.

[0082] Examples of electronically conductive materials that may be included in electrode materials include carbon black (such as Ketjen® carbon, acetylene black, etc.), graphite, graphene, carbon nanotubes, carbon fibers (including carbon nanofibers, vapor-grown carbon fibers (VGCF), etc.), non-powdered carbon obtained by carbonization of organic precursors (for example, as a coating on particles), or at least a combination of these.

[0083] Non-limiting examples of electrode material binders include the polymer binders mentioned above in relation to a thin layer of electrolyte or below, but also include rubber-type binders such as SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), and ACM (acrylate rubber), or fluorinated polymer binders such as PVDF (polyvinylidene fluoride) and PTFE (polytetrafluoroethylene), and combinations thereof. Some binders, such as rubber-type binders, may also include additives such as CMC (carboxymethylcellulose).

[0084] Lithium salts or ceramic or glass-type inorganic particles, or other additives such as other compatible active materials (e.g., sulfur), may also be present in the electrode material.

[0085] A metal film or electrode material can be applied to a current collector (e.g., aluminum, copper). In one example, the current collector is made of carbon-coated aluminum. In another alternative configuration, the electrodes may be self-supporting.

[0086] This specification also relates to the preparation process for the surface-modified electrodes described herein. This process comprises (i) mixing an inorganic compound and an optionally crosslinkable solvable polymer in a solvent, optionally including a salt and / or a crosslinking agent; (ii) spreading the mixture obtained in (i) onto the surface of an electrode; (iii) removing the solvent; and optionally (iv) crosslinking the polymer (e.g., ionically, thermally, or by irradiation). Steps (iii) and (iv) may optionally be reversed in order.

[0087] If the electrode is a metal film such as lithium, steps (ii), (iii), and / or (iv) are preferably carried out under vacuum or in an anhydrous chamber filled with an inert gas such as argon.

[0088] In an alternative configuration, if the polymer is crosslinkable and sufficiently liquid before crosslinking, the process can eliminate the presence of the solvent and step (iii) can be avoided.

[0089] The coating can be spread using conventional methods, such as using a roller (including the continuous roll-to-roll method) coated with the mixture, a doctor blade, spray coating, centrifugal separation, or printing.

[0090] The organic solvent used can be any solvent that is nonreactive with the metal film or electrode material. Examples include tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), heptane, toluene, or combinations thereof.

[0091] Solid electrode-electrolyte components are also considered herein. These include at least one multilayer material comprising an electrode film, a thin layer on the electrode film as described above, and a solid electrolyte film on the thin layer.

[0092] For example, the solid electrolyte comprises at least one solvating polymer and a lithium salt. The solvating polymer of the electrolyte may be selected from linear or branched polyether polymers (e.g., PEO, PPO, or EO / PO copolymers), poly(dimethylsiloxane), poly(alkylene carbonate), poly(alkylene sulfone), poly(alkylene sulfamide), polyurethane, poly(vinyl alcohol), polyacrylonitrile, poly(methyl methacrylate), and copolymers thereof, and the solvating polymer may optionally contain crosslinkable units and may be crosslinked as necessary. The lithium salts that may enter the solid electrolyte are as described for the thin layer. However, the salt of the solid electrolyte may be selected from the above, but may differ from or be identical to those present in the thin layer. It should be noted that this specification also considers the use of this electrode with gel-type or solid-type polymer electrolytes having properties similar to gel electrolytes.

[0093] In another example, solid electrolytes include ceramics combined with or uncombined with the polymers described in the previous paragraph. For example, the electrolyte is a composite material comprising a polymer and at least one ceramic, which may be as described with respect to thin layers. Solid electrolytes may also include ceramics without the use of polymers. Such ceramics include, for example, oxide ceramics (LAGP, LLZO, LATP, etc.) and sulfide ceramics (Li7P3S 11 Examples include glass ceramics and other similar ceramics.

[0094] The technology also relates to an electrochemical cell comprising a negative electrode, a positive electrode, and a solid electrolyte, wherein at least one of the electrodes is as described in this application.

[0095] For example, a cell contains the following elements stacked in order: - Metal films as electrode materials; - A thin layer containing an inorganic compound in a solvated polymer, as described herein and optionally crosslinked; - Solid electrolyte membrane; and - Electrode material films as described herein.

[0096] In another example, a cell contains the following elements stacked in order: - Metal films as electrode materials; - solid electrolyte membrane; - Thin layers containing inorganic compounds in solvated polymers described herein and optionally crosslinked; and - Electrode material films as described herein.

[0097] According to the third example, the cell contains the following elements stacked in order: - Metal films as electrode materials; - A thin layer containing an inorganic compound in a solvated polymer, as described herein and optionally crosslinked; - solid electrolyte membrane; - Thin layers containing inorganic compounds in solvated polymers described herein and optionally crosslinked; and - Electrode material films as described herein.

[0098] This specification relates to an electrochemical accumulator comprising at least one electrochemical cell as defined herein. For example, the electrochemical accumulator is a lithium or lithium-ion battery.

[0099] In another aspect, the electrochemical accumulator of this application is intended for use in portable devices, such as mobile phones, cameras, tablets or laptops, in electric or hybrid vehicles, or in renewable energy storage. [Examples]

[0100] The following non-limiting examples are illustrative embodiments and should not be construed as further limiting the scope of the invention. These embodiments are better understood by referring to the accompanying drawings. Example 1 - Modification of electrode surface (a) Mg2B2O5 (rods), polymers and lithium salts on lithium or alloys

[0101] A mixture containing 50% or 70% by weight of Mg2B2O5 (rod-shaped ceramic), with the remainder (50% or 30%) being a mixture of a salt (LiTFSI) with an atomic ratio of O:Li=20:1 and a PEO-based crosslinkable polymer, is prepared in tetrahydrofuran (THF). The entire mixture is dispersed in a disc mixer (Ultra-Turrax) until a stable suspension is obtained. The amount of THF is adjusted to the point where the appropriate viscosity is obtained and the ceramic precipitates at the bottom of the container. Typically, a dispersion containing about 20-25% by weight of the mixture "ceramic + polymer + salt + UV crosslinking agent" is prepared in the solvent and coated with lithium (pure Li) or Li by a doctor blade or spray coater. x M y Spread the material onto a sheet of a specific alloy (where x>y) (for example, a Li alloy containing Mg or Al). Then, place the lithium or lithium alloy sheet in a glass enclosure under vacuum, or in a chamber filled with an inert gas such as argon (avoid nitrogen as it reacts rapidly with lithium). Once the ambient air has been removed, a UV lamp is turned on over the metal film (on the side of the spread layer) to initiate crosslinking (typically at a distance of 30 cm and 300 WPI for 5 minutes). The lithium foil is then dried at 80°C under vacuum before use in a battery.

[0102] Instead of a UV crosslinking agent, a thermosetting agent can also be used. In this case, the lithium foil is left under vacuum at 80°C for at least one night and not treated under UV light. (b) Al2O3 (spherical), polymers and lithium salts on lithium or alloys

[0103] 85% by weight Al2O3 (approximately 10m 2A mixture containing ceramics in the form of small spheres with a small specific surface area of ​​1 / g, the remainder (15%) being a mixture of salt (LiTFSI) with an atomic ratio of O:Li=20:1 and a PEO-based crosslinkable polymer, is prepared in THF. The entire mixture is dispersed, and the amount of THF is adjusted as in (a). Typically, a dispersion containing 25-40 wt% of the mixture "ceramics + polymer + salt + heat or UV crosslinking agent" is prepared and spread onto lithium or lithium alloy foil with a doctor blade. Subsequently, the lithium (or alloy) foil containing the spread layer is placed directly into a vacuum oven to dry and crosslinked at 80°C for at least 15 hours before use in a battery. (c) Al2O3 (acinet), polymers and lithium salts on lithium or alloys

[0104] 50% by weight Al2O3 (specific surface area approximately 164 m²) 2 A mixture containing needle-shaped ceramic (1 / g), with the remainder (50%) consisting of a mixture of salt (LiTFSI) having an atomic ratio of O:Li=20:1 and a PEO-based crosslinkable polymer, is prepared in THF. The entire mixture is dispersed, and the amount of THF is adjusted as in (a). Typically, a dispersion containing about 25 wt% of the mixture "ceramic + polymer + salt + heat or UV crosslinking agent" is prepared and spread onto lithium (pure Li) or lithium alloy foil by spray coater. Subsequently, the lithium (or alloy) piece containing the spread layer is placed directly into a vacuum oven and dried at 80°C for at least 15 hours before use in a battery.

[0105] Various surface-modified electrodes were manufactured using the method described above and are summarized in Table 1. The average thickness of the ceramic polymer thin layer deposited on lithium or lithium alloy of these electrodes ranges from 4 μm to 7 μm. [Table 1]

[0106] For comparative purposes, two LiAl electrodes were also prepared, coated with ceramic and polymer mixtures having thicknesses of 15–20 μm (70% spherical Al2O3) and 10–15 μm (85% spherical Al2O3), respectively. The properties of these electrodes and the electrodes in Table 1 are described in detail in Example 2. (d) Al2O3 (spherical), polymer and lithium salt on LiFePO4

[0107] The LiFePO4 (LFP) electrode is prepared by mixing 73.5 wt% carbon-coated LFP P2 and 1 wt% Ketjen® ECP600 carbon with the remainder (25.5%), which is a mixture of polymer and LiFSI, and spreading it onto a carbon-coated aluminum current collector. The polymer is the same as that used for the thin layer of the metal electrode and has a molar ratio of O:Li = 20:1.

[0108] A mixture of ceramic-free polymer and LiTFSI (20:1) with a UV initiator was prepared in THF and then spread onto an LFP cathode by doctor blade. The cathode was then pre-dried in a 50°C oven for 5 minutes and then placed under a UV lamp (300 WPI) in a nitrogen atmosphere for 5 minutes. The polymer used was the same as that used for the thin layer of the metal electrode.

[0109] Using the same method, however, different layers were prepared containing ceramic (spherical Al2O3, 50 wt%) in the mixture from the previous paragraph. Tests were also conducted with different O:Li ratios (5:1, 10:1, 15:1, and 20:1). Better preparation of the suspension can improve the quality of the thin layers. Example 2 - Characteristics of the modified electrode (a) Modified metal electrodes

[0110] Figure 1 shows a cross-section of a metallic lithium piece with a ceramic thin layer (E1, 85% spherical Al2O3). The layer, although highly concentrated with ceramic, remains intact and does not collapse even during cutting.

[0111] Scanning electron microscope (SEM) images were taken to visualize different types of thin layers on lithium and its alloys.

[0112] There are two cases regarding the thin layer (approximately 5 μm) for which the inventors describe surface modification, and rather, a thin layer of approximately 15–25 μm, which is a solid polymer electrolyte (SPE) directly coated onto the lithium electrode. Electrochemical tests in both cases are shown below to demonstrate the importance of surface modification rather than the application of the SPE to the electrode.

[0113] Figure 2 shows a thin layer (E4, 50% by weight, 4–5 μm) of Mg2B2O5 ceramic on the surface of a LiAl alloy. Chemical mapping clearly shows the presence of sulfur (e) and fluorine (f) atoms due to the lithium salt, but the majority are magnesium (b) atoms originating from the extremely hard, rod-shaped ceramic, which gives the surface a somewhat uniform appearance.

[0114] By using nanometer-sized spherical Al2O3 spheres, the amount of ceramic can be easily increased to 85% to make the surface more uniform and make dendrite progression more difficult. Figure 3 shows a thin layer (85 wt%, 6-7 μm) of spherical Al2O3 ceramic on the surface of a LiMg alloy (E2). In the image on the right, two layers are clearly visible, one rich in polymer and ceramic, and the other very rich in ceramic. By taking advantage of the rapid sedimentation of ceramic when the ceramic is highly concentrated in the composition of the ink applied to lithium, a very dense ceramic layer can be formed on the lithium surface. The top layer is more polymer-rich and therefore more viscous, providing very good contact between the lithium and the solid polymer electrolyte (SPE) that is hot-laminated onto the thin layer.

[0115] Figure 4 shows another example of a thin layer with nanometer-sized needle-shaped Al2O3 particles on a LiAl alloy (E5). When combined with a polymer, very high-density aggregates are obtained, and due to the large specific surface area of ​​the ceramic, only 50 wt% of ceramic is used. Above 50 wt%, all the polymer is consumed to coat the particles, and the film formed on the lithium is no longer strong enough to withstand mechanical stress. The goal is to find the solubility limit of ceramic in polymer for forming a thin, strong film where the ceramic is most concentrated, and to obtain a “ceramic-in-polymer” type mixture, different from those usually reported for SPEs. In fact, rather than a small amount of ceramic, it is added to the SPE to disrupt the crystallinity of the polymer and create Lewis acid / base competition between the polymer, lithium ions, and oxygen-containing groups on the ceramic surface. The chemical mappings in Figures 4(b)–4(e) show that aluminum (c) is rich in small aggregates, and thus the oxygen (d) and carbon (e) signals are barely visible because the ceramic is well dispersed.

[0116] To compare the electrochemical performance of lithium with a ceramic thin layer and lithium with a SPE (approximately 20 μm thick) deposited on its surface, tests were also conducted on depositing SPE onto lithium. These lithium materials can be used directly with other electrodes by hot pressing them without adding any further SPE.

[0117] Figure 5 shows an example of a SPE approximately 15–20 μm in size, deposited directly on a LiAl lithium alloy and composed of spherical Al2O3 ceramic (70 wt%) in the polymer used in Example 1. Two distinct layers are visible, one rich in polymer and ceramic, and the other very rich in ceramic. The majority of this layer consists of ceramic particles (white), but in the lower layer, a darker area constituting the polymer is visible in the image above. Of course, such an SPE is not very effective against dendrites because the ceramic concentration is not sufficiently high, but it becomes more adhesive when assembled with another electrode.

[0118] Figure 6 shows another example of SPE (approximately 10–15 μm) deposited on the surface of a LiAl lithium alloy, this time with 85 wt% spherical Al2O3 ceramic particles in the same polymer. Here again, two layers are clearly visible, the first layer rich in polymer and ceramic, and the second layer very rich in ceramic. Due to the greater ceramic richness, the dark area seen in the lower layer is less compared to Figure 5. Thus, this type of SPE is more effective against dendrites than the example containing 70% ceramic. However, these last two layers, although thicker, are still not suitable for use as solid electrolytes because their surfaces are not sticky enough to adhere to the cathode. (b) Modified composite electrode

[0119] Electrodes (with and without ceramic) prepared according to Example 1(d) were analyzed. Figure 26 shows thin layers of polymer and salt without ceramic. The thickness of these layers is 4–5 μm. Figure 27 shows the chemical mapping of the electrode edge. Sulfur (f) in the salt and carbon (e) in the polymer are clearly visible.

[0120] Electrodes containing thin layers of spherical Al2O3 ceramic and polymer and lithium salt mixtures with different O:Li molar ratios (5:1, 10:1, 15:1, and 20:1) were also analyzed. Figure 28 shows a thin layer of polymer and salt (O:Li ratio 20:1) containing 50 wt% Al2O3 and having a thickness of approximately 5–5.5 μm. The chemical mapping of this same electrode is shown in Figure 29. Example 3 - Preparation of symmetrical or complete cells

[0121] Symmetrical Li / SPE / Li and complete LFP / SPE / Li cells were assembled. These cells were prepared using either the electrodes shown in Table 1 or the reference electrodes (without thin layers). The respective configurations are shown in Tables 2 and 3.

[0122] The electrolyte (SPE) is composed of a mixture of a salt (LiTFSI) with an atomic ratio of O:Li = 20:1 and a PEO-based crosslinkable polymer. This mixture is spread onto a substrate and crosslinked. The electrode is then hot-rolled onto the SPE at 80°C in an anhydrous chamber under vacuum, or in a glove box under argon in the case of lithium.

[0123] The LFP (LiFePO4) cathode consists of carbon-coated LFP P2 (75.3%), Ketjen® Black (1%), polymer (19.23%), and LiTFSI (6.27%). The polymer is the same as that used in thin layers and SPEs, with a molar ratio of O:Li = 20:1. [Table 2] [Table 3]

[0124] These cells were analyzed and then tested under cyclic conditions. The characteristics of these batteries are shown in the following examples. Example 4 - Characteristics of symmetrical or perfect cells (a) Symmetrical cell using unmodified lithium or lithium alloy

[0125] To compare with SEM images obtained using cells modified with a metal film (Li or Li alloy) using this method, SEM images of a symmetrical cell containing an unmodified metal film were taken.

[0126] Symmetrical Li / SPE / Li cells were also subjected to constant current cycling by applying various constant currents in the range of C / 24 to 1C. Cycleability testing was also performed by cycling at C / 4 until the battery was short-circuited. Cell impedance measurements were performed at 50°C. i. Using unmodified pure lithium (P(a) cell)

[0127] Figure 7 shows SEM images depicting the Li / SPE / Li stack after the decomposition of cycled and short-circuited cells. Dendrites are not visible in the cell cross-section analyzed by SEM, but may be present elsewhere within the cell. Note that the aluminum elements shown in the chemical mapping originate from the support structure behind the sample, not from the sample itself.

[0128] Impedance, cycle stability in the C / 4 regime, and resistance were measured at various applied currents. Testing four P(a) cells yielded relatively similar impedance curves (see Figure 8(a)). The charge transfer interface appeared less efficient, with larger half-arcs.

[0129] Next, the stability of the P(a) cells was tested. After two formation cycles at C / 24, the cells tested at C / 4 showed a rapid increase in potential, and in the fourth cycle, a sharp change was observed in response to the applied current, causing the battery to rapidly short circuit (see Figure 8(b)). In Figure 8(c), it is clearly visible that the other two P(a) cells do not resist for a very long period when the current at C / 6 is applied. ii. Unmodified LiAl lithium alloy is present (P(b) cell)

[0130] Figure 9(a) shows spectral impedance measurements performed at 50°C for four symmetrical P(b) cells assembled using standard LiAl alloy. Two of these identical cells were examined for cycle stability at the C / 4 rate (Figure 9(b)), and the other two were subjected to resistance tests at various applied currents (Figure 9(c), rate performance).

[0131] The impedances are very close across the four different P(b) cells, indicating repeatability in the assembly. After two formation cycles at C / 24, the cell tested at C / 4 shows a rapid rise in overpotential, with a sharp change in response to the applied current by the seventh cycle, causing the cell to rapidly short circuit. In Figure 9(c), it is clearly visible that the P(b) cell cannot withstand more than two cycles when the C / 6 current is applied. iii. Unmodified LiMg lithium alloy present (P(c) cell)

[0132] Figure 10 shows the same test as in Figure 9, except that a LiMg alloy was used. The charge transfer interface appears to have lower efficiency, and the semi-arc is larger. For the LiAl alloy, the battery was depleted in about 150 hours with a constant current of C / 4 and could not withstand the application of a current equivalent to C / 6. iv. SPEs containing unmodified LiAl and ceramics (P(d) cells)

[0133] Further electrochemical tests were conducted to demonstrate that surface modification of lithium (a thin layer of approximately 5 μm) is beneficial for improving the lifespan and cycle quality of lithium batteries. The lithium modified by the thin layer needs to be combined with a SPE and a cathode (the cathode itself may or may not contain a thin layer that may have the same properties). After rolling the stack at 80°C, the contact between the components is very good, and the ceramic-rich protective layer is retained on the lithium side.

[0134] For example, if you form an SPE containing a high percentage (e.g., 70%) of ceramic on a polypropylene film, then peel it off and laminate it between two lithium films, the experiment will not work because the SPE is not strong enough to adhere to the electrode film and is not tacky enough.

[0135] Another test, shown in Figure 21(a), involves directly depositing SPE onto lithium (see also Figures 5 and 6). If the thickness is too large, the SPE cannot be added, and this type of coating is not sufficiently tacky to make good contact with the second unmodified lithium. The impedance measurement in Figure 21(b) shows huge charge transfer resistance due to insufficient physical contact between the two lithiums and the coating, and an excess amount of ceramic which is detrimental in this scenario. As shown in Figure 21(c), the battery cannot be cycled and depleted prematurely. (b) Symmetrical cells with modified lithium or lithium alloy

[0136] SEM images of symmetric cells containing modified metal films were taken for comparison with SEM images obtained from cells without modified metal films (see (a)).

[0137] Surface-modified Li / SPE / Li symmetric cells were also subjected to constant current cycling by applying various constant currents in the range of C / 24 to 1C. Cycleability testing was also performed by cycling at C / 4 until the battery was short-circuited. Impedance measurements were performed on the cells at 50°C. i. LiAl lithium alloy modified with 85% spherical Al2O3 (P1 cell)

[0138] Figure 11 shows an SEM image of a stacked structure after cycling, consisting of two lithium (LiAl) elements coated with a 4 μm thin layer (85 mass%) of spherical Al2O3 ceramic. While no dendrites are visible, the P1 cell after short-circuiting is indicated. Even during cycling, the ceramic layer remains dense, providing protection that slows dendrite progression. At the highest magnification, it is clear that each ceramic particle (sphere) is coated with a polymer in a "polymer-in-ceramic" configuration, rather than ceramic embedded within a polymer as is commonly reported.

[0139] Figures 12(a) to 12(g) show SEM images and chemical mappings of the P1 cell, the latter clearly showing the Al2O3 layer. Locally, the ceramic layer is slightly deformed due to the repeated high-current cycling it has undergone.

[0140] Figure 13(a) clearly shows that the protected lithium in P1 can be cycled up to a 1C rate without short-circuiting under small overvoltages. Figures 13(b) and 13(c) show spectral impedance measurements performed at 50°C for two symmetric P1 cells after assembly and after each cycling rate. The impedance remains relatively stable during cycling, demonstrating that the lithium does not undergo strong deformation even when high currents are applied.

[0141] Figures 14(a) and 14(b) show the cycling of these same P1 cells at 1C over several cycles. Both batteries short-circuited during 320–360 hours of cycling, which represents a clear improvement over the results in Figure 9. Furthermore, the impedances shown in Figures 14(c) and 14(d) remain stable during high-current cycling at 1C (results shown every 3 cycles at 1C).

[0142] Figure 15 shows an example of a cell that has been cycled and short-circuited. The cell shown is the same cell whose cycling is shown in Figure 14(a). In this SEM image, the progress of two dendrite formations is clearly visible. Chemical mapping shows that the Al2O3 layer has been broken by the dendrites and is more severely fractured compared to what is seen in the SEM image of Figure 12. ii. Lithium modified with 85% spherical Al2O3 (P2 cell)

[0143] The P2 cells were also assembled using a thin layer containing pure lithium and 85% spherical Al2O3 ceramic. The electrochemical results are shown in Figure 16. The impedance was highly reproducible for the four assembled cells (Figure 16(a)). It took 300 to 350 hours for the cells to short-circuit under a constant current of C / 4 (Figure 16(b)), whereas before surface modification, the batteries were depleted in just 120 hours. Furthermore, the batteries could withstand high currents up to 1C and could be cycled for more than 300 hours (Figure 16(c)). iii. LiAl lithium alloy modified with 50% needle-shaped Al2O3 (P3 cell)

[0144] Very good results were obtained with P3 cells containing lithium coated with 50% Al2O3 in a needle-like morphology (see also SEM image in Figure 4). The electrochemical results for the LiAl alloy coated with 50% Al2O3 are shown in Figure 17. Figure 17(a) shows highly reproducible impedance for all three cells. In Figure 17(b), it can be seen that the battery life was extended eightfold, as the pre-modification version could only cycle for 50 hours at C / 4 compared to 400 hours in this case. The charge / discharge rate capability in Figure 17(c) shows a very low bias cycling profile, which demonstrates the stability of the interface between lithium and SPE. iv. LiAl modified with 50% needle-shaped Al2O3 and unmodified LiAl (P4 cell)

[0145] To highlight the formation of dendrites within the battery and emphasize the protective role of the ceramic thin layer, LiAl / SPE / LiAl cells coated on only one side with a thin layer of Al2O3 (needle-shaped, 50%) were assembled and cycled. Battery cycling was stopped before a short circuit, as shown in the cycling profile in Figure 18. Figure 18(a) shows the assembly performed to examine the effect of the protective layer on lithium deformation, and Figure 18(b) shows the impedance results for the four assembled batteries.

[0146] A cross-section of a battery cycled at a low current (C / 4, cell in Figure 18(c)) was observed by SEM, and the image is shown in Figure 19. Since there was no short circuit, both interfaces appeared intact and not excessively deformed. Conversely, in the cell cycled up to 1C (cell in Figure 18(d)), SEM observation and chemical mapping of the Li / SPE / Li stack shown in Figure 20 reveals significant deformation on the unprotected lithium side, along with the presence of deactivated lithium in the SPE. On the other hand, the lithium on the ceramic side remains intact, and the ceramic layer is not damaged. (c) Comparative study of complete LFP / SPE / Li cells

[0147] A full-cell electrochemical test was conducted using LiFePO4 (LFP) as the cathode material, and the positive effect of a thin layer (approximately 5 μm) on the lithium surface was confirmed. i. Complete cells containing LFP / SPE / LiAl (P(e), P5, and P6 cells)

[0148] The tests were performed under the same conditions on complete cells containing unmodified LiAl(P(e)), LiAl(P5) modified with 50% Al2O3 needle-shaped particles, and LiAl(P6) with 85% Al2O3 spherical particles.

[0149] Figure 22 shows that the first two charge / discharge curves are perfect, with little polarization and a very clear plateau at 3.5V when using the modified LiAl alloy (Figures 22(b) and (c)). Furthermore, the results are reproducible. For example, Figure 22(b) shows two batteries with overlapping curves. When using unmodified LiAl lithium, the results are less reproducible, as seen in Figure 22(a). The discharge capacity is also smaller, and the plateau is not very clear for all three cells.

[0150] Long-term C / 6 cycling studies were conducted on these different batteries. Their cycleability is shown in Figure 23(a) for unreformed lithium (P(e) cell), in Figure 23(b) for lithium with a layer containing 50% needle-shaped Al2O3 (P5 cell), and in Figure 23(c) for lithium with a layer containing 85% spherical Al2O3 (P6 cell). When reformed lithium is used, the cycling efficiency and Coulombic efficiency are far more stable. On the other hand, it has become clear that secondary reactions (deformation and lithium consumption) occur at the lithium level due to the low Coulombic efficiency of batteries assembled using unreformed LiAl. ii. Complete cells containing LFP / SPE / LiMg (P7 and P(f) cells)

[0151] In LiMg alloys modified with a ceramic thin layer (85% spherical Al2O3, P7 cell), very similar results were obtained compared to an equivalent battery with unmodified LiMg (P(f) cell). Figure 24 shows long-term cycling studies at C / 6 and C / 2 for LFP / SPE / LiMg batteries using unmodified LiMg (Figure 24(a)) and LFP / SPE / LiMg batteries modified with ceramic (Figure 24(b)). In this case as well, cycling is more stable after lithium modification, especially at C / 2. In fact, this rate is favorable for dendrite progression and therefore favorable for short-circuit formation. For example, in the P(f) battery with unmodified LiMg, after 45 cycles at C / 2, the Coulomb efficiency drops sharply, fluctuating around 40%, demonstrating dendrite formation. Conversely, in the C / 2 cycling of P7 in Figure 24(b), the Coulomb efficiency remains stable throughout the cycling. iii. Complete cells containing LFP / SPE / Li (P8 and P(g) cells)

[0152] Finally, tests using pure Li in P(g) (unreformed Li) and P8 (Li reformed with 85% spherical Al2O3) batteries also demonstrated the advantages of using surface-reformed lithium. Figure 25(a) shows the rapid capacity loss of both batteries assembled with unreformed pure Li, and the Coulomb efficiency is more volatile than when using pure Li lithium with a ceramic layer. In the cycling shown in Figure 25(b), it is relatively stable at first, then the capacity decreases due to the current interruption between cycles 45 and 55, and the cycling appears to be affected thereafter, but the Coulomb efficiency still remains at approximately 100%. iv. Complete cells containing LFP / SPE / LiAl (with modified LFP)

[0153] The LFP / SPE / Li coin cell was assembled as follows: - Standard unmodified LiAl anode; - A self-supporting SPE with a thickness of 20 μm, containing the polymer used in the thin layer and LiTFSI (O:Li ratio of 30:1); - An LFP cathode as described in Example 1(d), with or without a ceramic thin layer (50% Al2O3 and an O:Li ratio of 10:1).

[0154] Figures 30(a) and 30(b) show long-term cycling experiments (charge: C / 6, discharge: C / 3) and cycling at different rates, respectively, in a coin cell at 80°C.

[0155] Some modifications can be made to any of the embodiments described above without departing from the scope of the invention as considered. References, patents, or scientific documents referred to herein are incorporated in their entirety by reference for all purposes. The present invention provides, for example, the following items: (Item 1) An electrode comprising a metal film modified by a thin layer: - The metal film comprises lithium or a lithium-containing alloy, and the metal film comprises a first and a second surface; and - An electrode wherein the thin layer comprises an inorganic compound in a solvated polymer, the thin layer is disposed on the first surface of the metal film and has an average thickness of about 10 μm or less, and the inorganic compound is present in the thin layer at a concentration between about 40% and about 90% by weight. (Item 2) The electrode according to item 1, wherein the aforementioned polymer is crosslinked. (Item 3) The electrode according to item 1 or 2, wherein the metal film contains lithium with impurities in an amount of less than 1000 ppm (or less than 0.1% by weight). (Item 4) The electrode according to item 1 or 2, wherein the metal film comprises an alloy of lithium with an element selected from other alkali metals (such as Na, K, Rb, and Cs), alkaline earth metals (such as Mg, Ca, Sr, and Ba), rare earth metals (such as Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), zirconium, copper, silver, bismuth, cobalt, manganese, zinc, aluminum, silicon, tin, antimony, cadmium, mercury, lead, molybdenum, iron, boron, indium, thallium, nickel, and germanium (e.g., Zr, Cu, Ag, Bi, Co, Zn, Al, Si, Sn, Sb, Cd, Hg, Pb, Mn, B, In, Tl, Ni, or Ge). (Item 5) The electrode according to item 4, wherein the alloy contains at least 75% by weight of lithium, or lithium between 85% and 99.9% by weight. (Item 6) The electrode according to any one of items 1 to 5, wherein the metal film further includes a passivation layer on the first surface, and the first surface is in contact with the thin layer. (Item 7) The passivation layer is made of silane, phosphonate, borate or inorganic compound (LiF, Li 3 N, Li 3 P, LiNO 3 Li 3 PO 4 The electrode described in item 6, comprising a compound selected from (etc.). (Item 8) The electrode according to any one of items 1 to 7, wherein the first surface of the metal film is modified in advance by stamping. (Item 9) The electrode according to any one of items 1 to 10, wherein the inorganic compound is in the form of particles (for example, spherical, rod-shaped, needle-shaped, etc.). (Item 10) The electrode described in item 9, wherein the average particle size is less than 1 μm, less than 500 nm, or less than 300 nm, or less than 200 nm, or between 1 nm and 500 nm, or between 10 nm and 500 nm, or between 50 nm and 500 nm, or between 100 nm and 500 nm, or between 1 nm and 300 nm, or between 10 nm and 300 nm, or between 50 nm and 300 nm, or between 100 nm and 300 nm, or between 1 nm and 200 nm, or between 10 nm and 200 nm, or between 50 nm and 200 nm, or between 1 nm and 100 nm, or between 10 nm and 100 nm, or between 25 nm and 100 nm, or between 50 nm and 100 nm. (Item 11) The electrode according to item 9 or 10, wherein the inorganic compound includes a ceramic. (Item 12) The inorganic compound is Al 2 O 3 Mg 2 B 2 O 5 na 2 O·2B 2 O 3 xMgO·yB 2 O 3 ·zH 2 O, TiO 2 ZrO 2 ZnO, Ti 2 O 3 SiO 2 、Cr 2 O 3 CeO 2 、B 2 O 3 、B 2 O, SrBi 4 Ti 4 O 15 , LLTO, LLZO, LAGP, LATP, Fe 2 O 3 BaTiO 3 γ-LiAlO 2 Molecular sieves and zeolites (e.g., aluminosilicate, mesoporous silica), sulfide ceramics (Li 7 P 3 S 11 Electrodes as described in any one of items 9 to 11, selected from glass ceramics (such as LIPON), other ceramics, and combinations thereof. (Item 13) The electrode according to any one of items 9 to 12, wherein the inorganic compound particles further comprise organic groups covalently grafted onto their surfaces, for example, the groups being selected from crosslinkable groups (such as organic groups including acrylate functional groups, methacrylate functional groups, vinyl functional groups, glycidyl functional groups, mercapto functional groups, etc.), aryl groups, alkylene oxide groups or poly(alkylene oxide) groups, and other organic groups. (Item 14) The particles of the inorganic compound have a small specific surface area (for example, 80 m²). 2 Less than / g, or 40m 2 An electrode according to any one of items 9 to 13, having a content of less than / g. (Item 15) The electrode according to item 14, wherein the inorganic compound is present in the thin layer at a concentration between about 65% and about 90% by weight, or between about 70% and about 85% by weight. (Item 16) The particles of the inorganic compound have a large specific surface area (for example, 80 m²). 2 / g and above, or 120m 2 An electrode according to any one of items 9 to 13, having a value of (and / g or greater). (Item 17) The electrode according to item 16, wherein the inorganic compound is present in the thin layer at a concentration between about 40% and about 65% by weight, or between about 45% and about 55% by weight. (Item 18) The electrode according to any one of items 1 to 17, wherein the average thickness of the thin layer is between approximately 0.5 μm and approximately 10 μm, or between approximately 1 μm and approximately 10 μm, or between approximately 2 μm and approximately 8 μm, or between approximately 2 μm and approximately 7 μm, or between 2 μm and approximately 5 μm. (Item 19) The electrode according to any one of items 1 to 18, wherein the solvating polymer is selected from linear or branched polyether polymers (e.g., PEO, PPO, or EO / PO copolymers), poly(dimethylsiloxane), poly(alkylene carbonate), poly(alkylene sulfone), poly(alkylene sulfamide), polyurethane, poly(vinyl alcohol), polyacrylonitrile, poly(methyl methacrylate), and their copolymers, and optionally includes crosslinking units derived from crosslinkable functional groups (such as acrylate functional groups, methacrylate functional groups, vinyl functional groups, glycidyl functional groups, mercapto functional groups, etc.). (Item 20) The electrode according to any one of items 1 to 19, wherein the thin layer further comprises a lithium salt. (Item 21) The lithium salt is lithium hexafluorophosphate (LiPF 6 ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 2-trifluoromethyl-4,5-dicyano-imidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium tetrafluoroborate (LiBF 4 ), lithium bis(oxalato) borate (LiBOB), lithium nitrate (LiNO 3 ), lithium chloride (LiCl), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (LiClO) 4 ), Lithium hexafluoroarsenate (LiAsF 6 ), lithium trifluoromethanesulfonate (LiSO 3 CF 3 )(LiTf), Lithium fluoroalkyl phosphate Li[PF 3 (CF 2 CF 3 ) 3 ](LiFAP), Lithium tetrakis(trifluoroacetoxy)borate Li[B(OCOCF 3 ) 4 ](LiTFAB), Lithium bis(1,2-benzenediolato(2-)-O,O')borate Li[B(C 6 O 2 ) 2 Electrodes as described in item 20, selected from ](LBBB) and combinations thereof. (Item 22) The electrode according to any one of items 1 to 21, further comprising a current collector in contact with the second surface of the metal film. (Item 23) An electrode comprising an electrode material film modified by a thin layer: - The electrode material film comprises an electrochemical active material, optionally a binder, and optionally an electronically conductive material, and the electrode material film comprises a first and a second surface; and - An electrode wherein the thin layer comprises an inorganic compound in a solvated polymer, the thin layer is disposed on the first surface of the metal film and has an average thickness of about 10 μm or less, and the inorganic compound is present in the thin layer at a concentration between about 40% and about 90% by weight. (Item 24) The electrode according to item 23, wherein the aforementioned polymer is crosslinked. (Item 25) The electrode according to item 23 or 24, wherein the inorganic compound is in the form of particles (e.g., spherical, rod-shaped, needle-shaped, etc.). (Item 26) Electrodes as described in item 25, having an average particle size of less than 1 μm, less than 500 nm, or less than 300 nm, or less than 200 nm, or between 1 nm and 500 nm, or between 10 nm and 500 nm, or between 50 nm and 500 nm, or between 100 nm and 500 nm, or between 1 nm and 300 nm, or between 10 nm and 300 nm, or between 50 nm and 300 nm, or between 100 nm and 300 nm, or between 1 nm and 200 nm, or between 10 nm and 200 nm, or further between 50 nm and 200 nm, or between 100 nm and 200 nm, or between 1 nm and 100 nm, or further between 25 nm and 100 nm, or between 50 nm and 100 nm. (Item 27) The electrode according to item 25 or 26, wherein the inorganic compound includes a ceramic. (Item 28) The inorganic compound is Al 2 O 3 Mg 2 B 2 O 5 na 2 O·2B 2 O 3 xMgO·yB 2 O 3 ·zH 2 O, TiO 2 ZrO 2 ZnO, Ti 2 O 3 SiO 2 、Cr 2 O 3 CeO 2 、B 2 O 3 、B 2 O, SrBi 4 Ti 4 O 15 , LLTO, LLZO, LAGP, LATP, Fe 2 O 3 BaTiO 3 γ-LiAlO 2 Molecular sieves and zeolites (e.g., aluminosilicate, mesoporous silica), sulfide ceramics (Li 7 P 3 S 11 Electrodes as described in any one of items 25 to 27, selected from glass ceramics (such as LIPON), other ceramics, and combinations thereof. (Item 29) The electrode according to any one of items 25 to 28, wherein the inorganic compound particles further comprise organic groups covalently grafted onto their surfaces, for example, the groups being selected from crosslinkable groups (such as organic groups including acrylate functional groups, methacrylate functional groups, vinyl functional groups, glycidyl functional groups, mercapto functional groups, etc.), aryl groups, alkylene oxide groups or poly(alkylene oxide) groups, and other organic groups. (Item 30) The particles of the inorganic compound have a small specific surface area (for example, 80 m²). 2 Less than / g, or 40m 2 An electrode according to any one of items 25 to 29, having a content of less than / g. (Item 31) The electrode according to item 30, wherein the inorganic compound is present in the thin layer at a concentration between approximately 65% ​​and approximately 90% by weight, or between approximately 70% and approximately 85% by weight. (Item 32) The particles of the inorganic compound have a large specific surface area (for example, 80 m²). 2 / g and above, or 120m 2 An electrode according to any one of items 25 to 29, having a value of (and / g or greater). (Item 33) The electrode according to item 32, wherein the inorganic compound is present in the thin layer at a concentration between about 40% and about 65% by weight, or between about 45% and about 55% by weight. (Item 34) The electrode according to any one of items 23 to 33, wherein the average thickness of the thin layer is between approximately 0.5 μm and approximately 10 μm, or between approximately 1 μm and approximately 10 μm, or between approximately 2 μm and approximately 8 μm, or between approximately 2 μm and approximately 7 μm, or between 2 μm and approximately 5 μm. (Item 35) The electrode according to any one of items 23 to 34, wherein the solvating polymer is selected from linear or branched polyether polymers (e.g., PEO, PPO, or EO / PO copolymers), poly(dimethylsiloxane), poly(alkylene carbonate), poly(alkylene sulfone), poly(alkylene sulfamide), polyurethane, poly(vinyl alcohol), polyacrylonitrile, poly(methyl methacrylate), and their copolymers, and optionally includes crosslinking units derived from crosslinkable functional groups (such as acrylate functional groups, methacrylate functional groups, vinyl functional groups, glycidyl functional groups, mercapto functional groups, etc.). (Item 36) The electrode according to any one of items 23 to 35, wherein the thin layer further comprises a lithium salt. (Item 37) The lithium salt is lithium hexafluorophosphate (LiPF 6 ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 2-trifluoromethyl-4,5-dicyano-imidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium tetrafluoroborate (LiBF 4 ), lithium bis(oxalato) borate (LiBOB), lithium nitrate (LiNO 3 ), lithium chloride (LiCl), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (LiClO) 4 ), Lithium hexafluoroarsenate (LiAsF 6 ), lithium trifluoromethanesulfonate (LiSO 3 CF 3 )(LiTf), Lithium fluoroalkyl phosphate Li[PF 3 (CF 2 CF 3 ) 3 ](LiFAP), Lithium tetrakis(trifluoroacetoxy)borate Li[B(OCOCF 3 ) 4 ](LiTFAB), Lithium bis(1,2-benzenediolato(2-)-O,O')borate Li[B(C 6 O 2 ) 2 Electrodes as described in item 36, selected from ](LBBB) and combinations thereof. (Item 38) The electrode according to any one of items 23 to 37, further comprising a current collector in contact with the second surface of the electrode material film. (Item 39) The electrode according to any one of items 23 to 38, wherein the electrochemical active material is selected from metal phosphates, lithified metal phosphates, metal oxides, and lithified metal oxides. (Item 40) The electrochemical active material is LiM'PO 4 (In the formula, M' is Fe, Ni, Mn, Co, or a combination thereof.) LiV 3 O 8 、V 2 O 5 F, LiV 2 O 5 LiMn 2 O 4 , LiM''O 2 (In the formula, M'' is Mn, Co, Ni, or a combination thereof (NMC, LiMn) x Co y Ni z O 2 (In the equation, x+y+z=1, etc.) ), Li(NiM''')O 2 (In the formula, M''' is Mn, Co, Al, Fe, Cr, Ti, Zr, or a combination thereof.), carbon-based active materials such as sulfur, selenium, iodine, iron(III) fluoride, copper(II) fluoride, lithium iodide, and graphite, and organic cathode active materials (polyimide, poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PTMA), tetra-lithium perylene-3,4,9,10-tetracarboxylate (PTCLi 4 ), naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA), perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA), π-conjugated dicarboxylates, and anthraquinones, etc., or any combination of two or more of these materials, as per compatibility with each other, as described in any one of items 23 to 38. (Item 41) The electrode according to any one of items 23 to 40, wherein the electrochemical active material is in the form of particles coated as necessary (for example, by a polymer, ceramic, carbon, or a combination of two or more thereof). (Item 42) An electrode-electrolyte component comprising an electrode and a solid electrolyte as described in any one of items 1 to 41. (Item 43) The electrode-electrolyte component according to item 42, wherein the solid electrolyte comprises at least one solvating polymer and a lithium salt. (Item 44) The electrode-electrolyte component according to item 43, wherein the solvating polymer of the electrolyte is selected from linear or branched polyether polymers (e.g., PEO, PPO, or EO / PO copolymers) and optionally includes crosslinkable units, poly(dimethylsiloxane), poly(alkylene carbonate), poly(alkylene sulfone), poly(alkylene sulfamide), polyurethane, poly(vinyl alcohol), polyacrylonitrile, poly(methyl methacrylate), and copolymers thereof, and the solvating polymer is optionally crosslinked. (Item 45) The lithium salt is lithium hexafluorophosphate (LiPF 6 ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 2-trifluoromethyl-4,5-dicyano-imidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium tetrafluoroborate (LiBF 4 ), lithium bis(oxalato) borate (LiBOB), lithium nitrate (LiNO 3 ), lithium chloride (LiCl), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (LiClO) 4 ), Lithium hexafluoroarsenate (LiAsF 6 ), lithium trifluoromethanesulfonate (LiSO 3 CF 3 )(LiTf), Lithium fluoroalkyl phosphate Li[PF 3 (CF 2 CF 3 ) 3 ](LiFAP), Lithium tetrakis(trifluoroacetoxy)borate Li[B(OCOCF 3 ) 4 ](LiTFAB), Lithium bis(1,2-benzenediolato(2-)-O,O')borate Li[B(C 6 O 2 ) 2 ](LBBB), and combinations thereof, as described in item 43 or 44. (Item 46) The electrode-electrolyte component according to any one of items 42 to 45, wherein the solid electrolyte includes ceramic. (Item 47) An electrochemical cell comprising a negative electrode, a positive electrode, and a solid electrolyte, wherein the negative electrode is as described in any one of items 1 to 22. (Item 48) An electrochemical cell comprising a negative electrode, a positive electrode, and a solid electrolyte, wherein the positive electrode is described in any one of items 23 to 41. (Item 49) An electrochemical cell comprising a negative electrode, a positive electrode, and a solid electrolyte, wherein the negative electrode is as described in any one of items 1 to 22, and the positive electrode is as described in any one of items 23 to 41. (Item 50) The electrochemical cell according to any one of items 47 to 49, wherein the solid electrolyte comprises at least one solvating polymer and a lithium salt. (Item 51) The electrochemical cell according to item 50, wherein the solvating polymer of the electrolyte is selected from linear or branched polyether polymers (e.g., PEO, PPO, or EO / PO copolymers) and optionally includes crosslinkable units, poly(dimethylsiloxane), poly(alkylene carbonate), poly(alkylene sulfone), poly(alkylene sulfamide), polyurethane, poly(vinyl alcohol), polyacrylonitrile, poly(methyl methacrylate), and copolymers thereof, and the solvating polymer is optionally crosslinked. (Item 52) The lithium salt is lithium hexafluorophosphate (LiPF 6 ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 2-trifluoromethyl-4,5-dicyano-imidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium tetrafluoroborate (LiBF 4 ), lithium bis(oxalato) borate (LiBOB), lithium nitrate (LiNO 3 ), lithium chloride (LiCl), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (LiClO) 4 ), Lithium hexafluoroarsenate (LiAsF 6 ), lithium trifluoromethanesulfonate (LiSO 3 CF 3 )(LiTf), Lithium fluoroalkyl phosphate Li[PF 3 (CF 2 CF 3 ) 3 ](LiFAP), Lithium tetrakis(trifluoroacetoxy)borate Li[B(OCOCF 3 )4 ](LiTFAB), Lithium bis(1,2-benzenediolato(2-)-O,O')borate Li[B(C 6 O 2 ) 2 ](LBBB), and combinations thereof, as described in item 50 or 51. (Item 53) The electrochemical cell according to any one of items 47 to 52, further comprising a ceramic solid electrolyte. (Item 54) An electrochemical accumulator comprising at least one electrochemical cell as described in any one of items 47 to 53. (Item 55) The electrochemical accumulator according to item 54, wherein the electrochemical accumulator is a lithium battery or a lithium-ion battery. (Item 56) Use of electrochemical accumulators as described in item 54 or 55 in portable devices, electric or hybrid vehicles, or renewable energy storage. (Item 57) The use described in item 56, wherein the portable device is selected from a mobile phone, camera, tablet, and laptop.

Claims

1. An electrode-electrolyte component comprising an electrode and a solid electrolyte, wherein the electrode comprises a metal film modified by a thin layer, - The metal film comprises lithium or a lithium-containing alloy, and the metal film comprises a first and a second surface; - The thin layer comprises an inorganic compound in a solvated polymer, the thin layer is positioned on the first surface of the metal film and has an average thickness of 0.5 μm to 10 μm, the inorganic compound is in the form of particles and is present in the thin layer at a concentration between 40% and 90% by weight; and The solvating polymer is selected from linear or branched polyether polymers, poly(dimethylsiloxane), poly(alkylene carbonate), poly(alkylene sulfone), poly(alkylene sulfamide), polyurethane, poly(vinyl alcohol), and copolymers thereof. Electrode-electrolyte component.

2. The aforementioned metal film Lithium containing impurities of less than 1000 ppm (or less than 0.1% by weight), An alloy of lithium with an element selected from alkali metals other than lithium, alkaline earth metals, rare earth metals, zirconium, copper, silver, bismuth, cobalt, manganese, zinc, aluminum, silicon, tin, antimony, cadmium, mercury, lead, molybdenum, iron, boron, indium, thallium, nickel, and germanium, wherein the alloy contains at least 75% by weight of lithium, or lithium between 85% and 99.9% by weight. The electrode-electrolyte component according to claim 1, comprising:

3. The electrode-electrolyte component according to claim 1 or 2, wherein the metal film further comprises a passivation layer on the first surface, the first surface being in contact with the thin layer via the passivation layer, and the passivation layer comprises a compound selected from silane, phosphonate, borate, or inorganic compounds.

4. The electrode-electrolyte component according to any one of claims 1 to 3, wherein the first surface of the metal film is modified in advance by stamping.

5. The electrode-electrolyte component according to any one of claims 1 to 4, further comprising a current collector that contacts the second surface of the metal film.

6. An electrode-electrolyte component comprising an electrode and a solid electrolyte, wherein the electrode comprises an electrode material film modified by a thin layer, - The electrode material film comprises an electrochemically active material in the form of particles, and the electrode material film comprises a first and a second surface; - The thin layer comprises an inorganic compound in a solvated polymer, the thin layer is positioned on the first surface of the electrode material film and has an average thickness of 0.5 μm to 10 μm, the inorganic compound is in the form of particles and is present in the thin layer at a concentration between 40% and 90% by weight; and The solvating polymer is selected from linear or branched polyether polymers, poly(dimethylsiloxane), poly(alkylene carbonate), poly(alkylene sulfone), poly(alkylene sulfamide), polyurethane, poly(vinyl alcohol), and copolymers thereof. Electrode-electrolyte component.

7. The electrode-electrolyte component according to claim 6, further comprising a binder, an electronically conductive material, or a combination thereof.

8. The electrode-electrolyte component according to claim 6 or 7, further comprising a current collector that contacts the second surface of the electrode material film.

9. The electrochemical active material is Selected from metal phosphates, lithium metal phosphates, metal oxides, and lithium metal oxides, The electrode-electrolyte component according to any one of claims 6 to 8.

10. The electrode-electrolyte component according to claim 9, wherein the electrochemical active material is LiM'PO₄ (wherein M' is Fe, Ni, Mn, Co, or a combination thereof), LiV₃O₸, V₂O₅F, LiV₂O₅, LiMn₂O₄, LiM''O₂ (wherein M'' is Mn, Co, Ni, or a combination thereof), LiMn x Co y Ni z O₂ (wherein x + y + z = 1), Li(NiM''')O₂ (wherein M''' is Mn, Co, Al, Fe, Cr, Ti, Zr, or a combination thereof), or a combination thereof.

11. The electrode-electrolyte component according to any one of claims 6 to 10, wherein the electrochemical active material is in the form of particles coated with a polymer, ceramic, carbon, or a combination of two or more thereof.

12. The electrode-electrolyte component according to any one of claims 1 to 11, wherein the particles of the inorganic compound have an average particle size between 1 nm and 500 nm, between 10 nm and 500 nm, between 50 nm and 500 nm, between 100 nm and 500 nm, between 1 nm and 300 nm, between 10 nm and 300 nm, between 50 nm and 300 nm, between 100 nm and 300 nm, between 1 nm and 200 nm, between 10 nm and 200 nm, between 50 nm and 200 nm, between 1 nm and 100 nm, between 10 nm and 100 nm, between 25 nm and 100 nm, or between 50 nm and 100 nm.

13. The inorganic compound containing ceramics, or Al ２ O ３ 、Mg ２ B ２ O ５ 、Na ２ O·2B ２ O ３ 、xMgO·yB ２ O ３ ·zH ２ O、TiO ２ 、ZrO ２ 、ZnO、Ti ２ O ３ 、SiO ２ 、Cr ２ O ３ 、CeO ２ 、B ２ O ３ 、B ２ O、SrBi ４ Ti ４ O １５ 、LLTO、LLZO、LAGP、LATP、Fe ２ O ３ 、BaTiO ３ 、γ-LiAlO ２ 、selected from molecular sieves and zeolites, sulfide ceramics, and glass ceramics, and combinations thereof The electrode-electrolyte component according to any one of claims 1 to 12.

14. The electrode-electrolyte component according to claim 12 or 13, wherein the inorganic compound particles further comprise organic groups covalently grafted onto their surfaces, for example, the groups being selected from crosslinkable groups, aryl groups, and alkylene oxide groups or poly(alkylene oxide) groups.

15. The particles of the inorganic compound have a specific surface area of ​​less than 80 m² / g, and the inorganic compound is present in the thin layer at a concentration between 65% and 90% by weight, or between 70% and 85% by weight, or The electrode-electrolyte component according to any one of claims 12 to 14, wherein the particles of the inorganic compound have a specific surface area of ​​at least 80 m² / g, and the inorganic compound is present in the thin layer at a concentration between 40% and 65% by weight, or between 45% and 55% by weight.

16. The electrode-electrolyte component according to any one of claims 1 to 15, wherein the average thickness of the thin layer is between 1 μm and 10 μm, between 2 μm and 8 μm, between 2 μm and 7 μm, or between 2 μm and 5 μm.

17. The electrode-electrolyte component according to any one of claims 1 to 16, wherein the solvating polymer is selected from linear or branched polyether polymers.

18. The electrode-electrolyte component according to any one of claims 1 to 17, wherein the solvating polymer is crosslinked.

19. The electrode-electrolyte component according to any one of claims 1 to 18, wherein the thin layer further comprises a lithium salt.

20. The lithium salt is lithium hexafluorophosphate (LiPF) ６ ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 2-trifluoromethyl-4,5-dicyanoimidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium tetrafluoroborate (LiBF ４ ), lithium bis(oxalato) borate (LiBOB), lithium nitrate (LiNO) ３ ), lithium chloride (LiCl), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (LiClO) ４ ), lithium hexafluoroarsenate (LiAsF ６ ), lithium trifluoromethanesulfonate (LiSO ３ CF ３ ) (LiTf), lithium fluoroalkyl phosphate Li[PF ３ (CF ２ CF ３ ) ３ ] (LiFAP), Lithium tetrakis(trifluoroacetoxy) borate Li[B(OCOCF ３ ) ４ ](LiTFAB), lithium bis(1,2-benzenediolato(2-)-O,O')borate Li[B(C ６ O ２ ) ２ The electrode-electrolyte component according to claim 19, selected from ] (LBBB) and combinations thereof.

21. An electrochemical cell comprising a negative electrode, a positive electrode, and a solid electrolyte, wherein the negative electrode or the positive electrode, together with the electrolyte, is an electrode-electrolyte component according to any one of claims 1 to 20.

22. The electrochemical cell according to claim 21, wherein the solid electrolyte comprises at least one solvating polymer and a lithium salt.

23. The electrochemical cell according to claim 22, wherein the solvating polymer of the electrolyte is selected from linear or branched polyether polymers, poly(dimethylsiloxane), poly(alkylene carbonate), poly(alkylene sulfone), poly(alkylene sulfamide), polyurethane, poly(vinyl alcohol), polyacrylonitrile, poly(methyl methacrylate), and copolymers thereof.

24. The lithium salt is lithium hexafluorophosphate (LiPF) ６ ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 2-trifluoromethyl-4,5-dicyanoimidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium tetrafluoroborate (LiBF ４ ), lithium bis(oxalato) borate (LiBOB), lithium nitrate (LiNO) ３ ), lithium chloride (LiCl), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (LiClO) ４ ), lithium hexafluoroarsenate (LiAsF ６ ), lithium trifluoromethanesulfonate (LiSO ３ CF ３ ) (LiTf), lithium fluoroalkyl phosphate Li[PF ３ (CF ２ CF ３ ) ３ ] (LiFAP), Lithium tetrakis(trifluoroacetoxy) borate Li[B(OCOCF ３ ) ４ ](LiTFAB), lithium bis(1,2-benzenediolato(2-)-O,O')borate Li[B(C ６ O ２ ) ２ An electrochemical cell according to claim 22 or 23, selected from ] (LBBB) and combinations thereof.

25. The electrochemical cell according to any one of claims 21 to 24, wherein the solid electrolyte further comprises a ceramic.

26. An electrochemical accumulator comprising at least one electrochemical cell as described in any one of claims 21 to 25.

27. Use of the electrochemical accumulator according to claim 26 in a portable device, in an electric or hybrid vehicle, or in renewable energy storage.

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